Engineering topics

Brooks, Scott C.

Publications and source records attributed to Brooks, Scott C..

13 records

DOE OSTI2024

Self‐Potential Tomography Preconditioned by Particle Swarm Optimization—Application to Monitoring Hyporheic Exchange in a Bedrock River

Abstract A self‐potential (SP) data‐inversion algorithm was developed and tested on an analytical model of electrical‐potential profile data attributed to single and multiple polarized electrical sources. The developed algorithm was then validated by an application to SP‐monitoring field data measured on the floodplain of East Fork Poplar Creek, Oak Ridge, Tennessee, to image electrical sources in areas conducive to preferential flow into the flood plain from the bedrock‐lined riverbed. The algorithm combined stochastic source‐localization by particle‐swarm‐optimization (PSO) of electrical sources characterized by simplified geometries with source tomography by regularized weighted least‐squares minimization of a quadratic objective function. Prior information was incorporated by preconditioning the tomography algorithm by PSO results. Variable percentages of random noise were added to analytical‐model data to evaluate the algorithm performance. Results indicated that true parameters of single‐source models were inverted and approximated with small residual error, whereas inversion of analytical‐model data representing multiple electrical sources accurately approximated the locations of the sources but miscalculated some parameters because of the non‐uniqueness of the inverse‐model solution. Source tomography applied to analytical model data during testing produced a spatially continuous parameter field that identified the locations of point‐scale synthetic dipole sources of electrical current flow with varying degrees of accuracy depending on the prior information incorporated into the tomography. When applied to SP‐monitoring field data, the algorithm imaged electrical sources within a known fault that intersects the bedrock riverbed and flood plain of East Fork Poplar Creek and depicted dynamic electrical conditions attributed to hyporheic exchange.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Rogers Quarry Special Studies Report 2024

Rogers Quarry (RQ) has a history of elevated selenium (Se) concentrations in water and fish caused by inputs from the Y-12 National Security Complex Filled Coal Ash Pond (FCAP). Selenium is acutely toxic at high concentrations, and chronic toxicity occurs at low aqueous concentrations because Se bioaccumulates in fish tissues. The US Environmental Protection Agency (EPA) recently developed water quality criteria for Se that include fish tissue as well as aqueous Se concentrations. The water column concentration criterion is 1.5 µg L -1 for lentic ecosystems and 3.1 µg L -1 for lotic ecosystems. The fish tissue criteria include both an egg/ovary concentration (15.1 µg/g dry weight) and a concentration for whole-body (8.5 µg/g dry weight) or fish muscle (11.3 µg/g dry weight). The egg/ovary criterion supersedes the fillet and aqueous concentrations if measured because Se toxicity manifests via reproductive effects in birds and fish. It is maternally transferred through eggs, leading to teratogenicity (i.e., deformities, developmental effects) in young fish. Historical bioaccumulation data suggest that Se is likely the primary contaminant of concern in RQ, but more recent sampling shows that aqueous As concentrations have been elevated in upper McCoy Branch (MB) leading to RQ. More recently, Se concentrations in fish collected from upper MB were found to be above the tissue criterion for Se for whole-body fish. In FY 2019, actions were taken to deepen the constructed wetland just downstream of the FCAP to increase its ability to remove coal ash particulates from the water column before water enters MB. Sampling was conducted throughout MB in FY 2020-2024 to evaluate the effectiveness of the actions taken in the FCAP wetland and to measure Se concentrations in biota throughout the watershed. The methods and results from a water and fish field collection campaign in April 2024 are presented in this report.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Comparison of machine learning and electrical resistivity arrays to inverse modeling for locating and characterizing subsurface targets

Here, this study evaluates the performance of multiple machine learning (ML) algorithms and electrical resistivity (ER) arrays for inversion with comparison to a conventional Gauss-Newton numerical inversion method. Four different ML models and four arrays were used for the estimation of only six variables for locating and characterizing hypothetical subsurface targets. The combination of dipole-dipole with Multilayer Perceptron Neural Network (MLP-NN) had the highest accuracy. Evaluation showed that both MLP-NN and Gauss-Newton methods performed well for estimating the matrix resistivity while target resistivity accuracy was lower, and MLP-NN produced sharper contrast at target boundaries for the field and hypothetical data. Both methods exhibited comparable target characterization performance, whereas MLP-NN had increased accuracy compared to Gauss-Newton in prediction of target width and height, which was attributed to numerical smoothing present in the Gauss-Newton approach. MLP-NN was also applied to a field dataset acquired at U.S. DOE Hanford site.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2024

Non-mercury methylating microbial taxa are integral to understanding links between mercury methylation and elemental cycles in marine and freshwater sediments

The goal of this study was to explore the role of non-mercury (Hg) methylating taxa in mercury methylation and to identify potential links between elemental cycles and Hg methylation. Statistical approaches were utilized to investigate the microbial community and biochemical functions in relation to methylmercury (MeHg) concentrations in marine and freshwater sediments. Sediments were collected from the methylation zone (top 15 cm) in four Hg-contaminated sites. Both abiotic (e.g., sulfate, sulfide, iron, salinity, total organic matter, etc.) and biotic factors (e.g., hgcA, abundances of methylating and non-methylating taxa) were quantified. Random forest and stepwise regression were performed to assess whether non-methylating taxa were significantly associated with MeHg concentration. Co-occurrence and functional network analyses were constructed to explore associations between taxa by examining microbial community structure, composition, and biochemical functions across sites. Regression analysis showed that approximately 80% of the variability in sediment MeHg concentration was predicted by total mercury concentration, the abundances of Hg methylating taxa, and the abundances of the non-Hg methylating taxa. The co-occurrence networks identified Paludibacteraceae and Syntrophorhabdaceae as keystone non Hg methylating taxa in multiple sites, indicating the potential for syntrophic interactions with Hg methylators. Strong associations were also observed between methanogens and sulfate-reducing bacteria, which were likely symbiotic associations. The functional network results suggested that non-Hg methylating taxa play important roles in sulfur respiration, nitrogen respiration, and the carbon metabolism-related functions methylotrophy, methanotrophy, and chemoheterotrophy. Interestingly, keystone functions varied by site and did not involve carbon- and sulfur-related functions only. In conclusion, our findings highlight associations between methylating and non-methylating taxa and sulfur, carbon, and nitrogen cycles in sediment methylation zones, with implications for predicting and understanding the impact of climate and land/sea use changes on Hg methylation.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2023

Towards Development of a Conceptual Model for Mercury in Bear Creek, Oak Ridge, Tennessee (FY23 Update)

Mercury concentrations in fish in Bear Creek are elevated and comparable to concentrations seen in fish in East Fork Poplar Creek (EFPC) on the Oak Ridge Reservation, even though aqueous inorganic mercury concentrations are orders of magnitude lower in Bear Creek than in EFPC. Acknowledging that the relationship between aqueous and fish tissue mercury concentrations is not linear, and that methylmercury (MeHg) concentrations are likely more related to fish tissue concentrations than aqueous total mercury (Hg T ) concentrations, MeHg production is not easily predicted or controlled. In Bear Creek, where aqueous Hg T concentrations are low, factors other than mercury loading drive the transformation of mercury to MeHg and subsequent trophic transfer to fish. Initial development of a waste disposal facility (Environmental Management Disposal Facility; EMDF) in Bear Creek Valley has begun, and operation of the EMDF has the potential to increase mercury inputs to Bear Creek. Consequently, understanding the factors contributing to elevated MeHg concentrations in water and fish in Bear Creek has increased relevance and importance. This report summarizes data from recent and historical compliance and investigatory studies with an eye toward building a conceptual model to understand the processes affecting mercury transport and transformation in the Bear Creek watershed, as well as to highlight key knowledge gaps in our understanding of these processes that warrant further investigation. The conceptual model will provide a strong technical basis for prioritizing and optimizing potential mitigation actions or best management practices to minimize potential negative effects of the EMDF related to mercury in Bear Creek.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2023

Rogers Quarry Special Studies Report 2023

Rogers Quarry (RQ) has a history of elevated Se concentrations in water and fish caused by inputs from the Y-12 National Security Complex Filled Coal Ash Pond (FCAP). Selenium is acutely toxic at high concentrations, and chronic toxicity occurs at low aqueous concentrations because Se bioaccumulates in fish tissues. The US Environmental Protection Agency (EPA) recently developed water quality criteria for Se that include fish tissue as well as aqueous Se concentrations. The water column concentration criterion is 1.5 µg L -1 for lentic ecosystems and 3.1 µg L -1 for lotic ecosystems. The fish tissue criteria include both an egg/ovary concentration (15.1 μg/g dry weight) and a concentration for whole-body (8.5 μg/g dry weight) or fish muscle (11.3 μg/g dry weight). The egg/ovary criterion supersedes the fillet and aqueous concentrations if measured because Se toxicity manifests via reproductive effects in birds and fish. It is maternally transferred through eggs, leading to teratogenicity (i.e., deformities, developmental effects) in young fish.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2023

Geoelectric Characterization of Hyporheic Exchange Flow in the Bedrock‐Lined Streambed of East Fork Poplar Creek, Oak Ridge, Tennessee

Abstract A multimethod geoelectric survey was implemented between January and March 2022 along a 220‐m long reach of the bedrock‐lined streambed of East Fork Poplar Creek in Oak Ridge, Tennessee to identify locations of surface‐water and groundwater exchange and characterize the subsurface flow paths that convey water between the stream and flood plain. A waterborne self‐potential (WaSP) survey was completed in January 2022 to measure the electric streaming‐potential field in the stream. Electric resistivity tomography (ERT) was performed in March 2022 on the flood plain adjacent to the WaSP survey reach to map the electric resistivity distribution and characterize the hydrogeology and subsurface flow paths that facilitate surface‐water and groundwater exchange in the bedrock‐lined stream. The combination of WaSP and ERT data support the qualitative interpretation that surface‐water and groundwater exchange likely occurs along fractures in outcropping bedrock and along two fault lines that intersect the limestone creek bed.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2023

Use of Stable Mercury Isotopes to Assess Mercury and Methylmercury Transformation and Transport across Critical Interfaces from the Molecular to the Watershed Scale (Final Report)

This project titled “Use of Stable Mercury Isotopes to Assess Mercury and Methylmercury Transformation and Transport across Critical Interfaces from the Molecular to the Watershed Scale” represents a collaborative effort between the University of Michigan (Jason Demers, PI) and Oak Ridge National Laboratory (Scott Brooks, co-I). Much has been learned about mercury (Hg) cycling in stream ecosystems, and East Fork Poplar Creek (EFPC) in particular, through decades of previous research. Nevertheless, some of the most fundamental questions regarding the sources of bioavailable Hg and its transformation to toxic methylmercury (MeHg) have remained unanswered. These fundamental questions include: (1) what are the sources and biogeochemical processes that lead to the input of dissolved Hg to stream water across critical subsurface interfaces within stream ecosystems, and EFPC in particular? and (2) what are the sources and biogeochemical processes that control the production and fate of bioaccumulative MeHg within stream ecosystems, and in EFPC in particular? To address these fundamental questions, our project aimed to couple laboratory experiments and field observations, both utilizing natural abundance Hg stable isotope techniques, to identify the processes responsible for generating mobile, bioavailable dissolved Hg from recalcitrant legacy sources within critical subsurface zones (e.g., streambed hyporheic zone, riparian floodplain subsurface). We used the isotopic signature of this bioavailable dissolved Hg to track its mobilization across these critical interfaces in order to link diffuse subsurface sources of dissolved Hg with increases in surface water dissolved Hg flux measured at the watershed scale. Additionally, our research aimed to determine the isotopic composition of MeHg within these same critical subsurface zones. We directly assessed the isotopic composition of MeHg within biota in order to gain insight into which subsurface sources of inorganic Hg and toxic MeHg are available for bioaccumulation within the EFPC ecosystem. Net fluxes of dissolved Hg along the flow path of EFPC were shown to vary spatially and temporally. In the Upper EFPC, within the Y12 boundary, stream water flux of dissolved Hg consistently decreased between the outfall and the downstream boundary of Y12 (57% ± 29%, 1SD). Within the Upper EFPC, an assessment of Hg isotopic composition suggested that losses were strongly reaction-driven, although isotopic diagnostics did not conform to any known processes. Downstream of Y12, in the upper reach of the Lower EFPC, dissolved Hg fluxes tended to increase during the dormant season (net gain of 11-120%), and decrease during the growing season (net loss of 23% +/- 18%, 1SD). In the downstream-most reach of Lower EFPC, dissolved Hg fluxes increased by 12-108% in 9 out of 10 monthly assessments. Overall, diffuse fluxes from the non-Y12 watershed accounted for 34% (+/- 17%, 1SD) of all dissolved Hg exported during base flow. Within Lower EFPC, an assessment of Hg isotopic composition was consistent with the contribution of diffuse Hg inputs from high-concentration hotspots within riparian floodplains and streambed hyporheic pore water. To investigate remobilization of recalcitrant Hg from legacy sediment sources, we developed procedures that coupled isotopic analysis with sequential extractions of streambed sediment. We found that the proportion of weakly-bound Hg within EFPC streambed sediment was relatively small, but could still account for a large proportion of the annual flux of dissolved Hg from EFPC. These sequential extractions also showed that this weakly-bound Hg fraction could be replenished from the much larger fraction of recalcitrant Hg in sediment. The isotopic composition of these weakly-bound and remobilized recalcitrant Hg fractions within the sediment was consistent with high-concentration dissolved Hg hotspots within hyporheic pore water. Thus, this research provided novel evidence that legacy mercury sources within streambed sediment could provide an ongoing contribution of dissolved Hg to surface waters. Finally, we developed new methods for the direct determination of the MeHg isotopic composition of organisms, which allowed a more direct evaluation of inorganic Hg and MeHg sources accumulating in the food web. We found that fish and aquatic invertebrates in both EFPC and a regional background site obtained inorganic Hg and MeHg from multiple isotopically distinct sources, including sediment, suspended particulates, and periphyton. Photodemethylation was found to be an important reaction influencing MeHg dynamics at both sites. However, the balance of microbial methylation and demethylation processes differed between the two streams, with fractionation resulting from methylation and demethylation processes being relatively in balance within the regional background site, whereas microbial methylation appeared to be dominant over microbial demethylation within the EFPC ecosystem. Broadly, the application of Hg isotopic analysis in this study led to numerous novel insights regarding the biogeochemical cycling of Hg in stream ecosystems. This research project promoted the development of two new approaches, including the coupling of sequential extractions with Hg isotopic analysis to assess remobilization of recalcitrant Hg within sediments, and a new method for the isotopic analysis of MeHg isolated from environmental samples. Both of these efforts represent advances in capacity for the field of mercury isotopic analysis and environmental assessment. Overall, this study demonstrates that the application of Hg stable isotope techniques continues to provide new insights into the biogeochemical cycling of Hg in complex aquatic environments, both within the EFPC and beyond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Determining the biogeochemical transformations of organic matter composition in rivers using molecular signatures

Inland waters are hotspots for biogeochemical activity, but the environmental and biological factors that govern the transformation of organic matter (OM) flowing through them are still poorly constrained. Here we evaluate data from a crowdsourced sampling campaign led by the Worldwide Hydrobiogeochemistry Observation Network for Dynamic River Systems (WHONDRS) consortium to investigate broad continental-scale trends in OM composition compared to localized events that influence biogeochemical transformations. Samples from two different OM compartments, sediments and surface water, were collected from 97 streams throughout the Northern Hemisphere and analyzed to identify differences in biogeochemical processes involved in OM transformations. By using dimensional reduction techniques, we identified that putative biogeochemical transformations and microbial respiration rates vary across sediment and surface water along river continua independent of latitude (18°N–68°N). In contrast, we reveal small- and large-scale patterns in OM composition related to local (sediment vs. water column) and reach (stream order, latitude) characteristics. These patterns lay the foundation to modeling the linkage between ecological processes and biogeochemical signals. We further showed how spatial, physical, and biogeochemical factors influence the reactivity of the two OM pools in local reaches yet find emergent broad-scale patterns between OM concentrations and stream order. OM processing will likely change as hydrologic flow regimes shift and vertical mixing occurs on different spatial and temporal scales. As our planet continues to warm and the timing and magnitude of surface and subsurface flows shift, understanding changes in OM cycling across hydrologic systems is critical, given the unknown broad-scale responses and consequences for riverine OM.

rivers↗

DOE OSTI2022

Coupling of nitric acid digestion and anion-exchange resin separation for the determination of methylmercury isotopic composition within organisms

Isotope ratios of methylmercury (MeHg) within organisms can be used to identify sources of MeHg that have accumulated in food webs, but these isotopic compositions are masked in organisms at lower trophic levels by the presence of inorganic mercury (iHg). To facilitate measurement of MeHg isotope ratios in organisms, we developed a method of extracting and isolating MeHg from fsh and aquatic invertebrates for compound-specifc isotopic analysis involving nitric acid digestion, batch anion-exchange resin separation, and pre-concentration by purge and trap. Recovery of MeHg was quantifed after each step in the procedure, and the average cumulative recovery of MeHg was 93.4±2.9% (1 SD, n=28) for biological reference materials and natural biota samples and 96.9±1.8% (1 SD, n=5) for aqueous MeHgCl standards. The amount of iHg impurities was also quantifed after each step, and the average MeHg purity was 97.8±4.3% (1 SD, n=28) across all reference materials and natural biota samples after the fnal separation step. Measured MeHg isotopic compositions of reference materials agreed with literature values obtained using other MeHg separation techniques, and MeHg isotope ratios of aqueous standards, reference materials, and natural biota samples were reproducible. On average, the reproducibility associated with reference material process replicates (2 SD) was 0.10‰ for δ 202 MeHg and 0.04‰ for Δ 199 MeHg. This new method provides a streamlined, reliable technique that utilizes a single sample aliquot for MeHg concentration and isotopic analysis. Furthermore, this promotes a tight coupling between MeHg concentration, %MeHg, and Hg isotopic composition, which may be especially benefcial for studying complex food webs with multiple isotopically distinct sources of iHg and/or MeHg.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Transient Storage Model Parameter Optimization Using the Simulated Annealing Method

Hyporheic exchange in streams is critical to ecosystem functions such as nutrient cycling along river corridors, especially for slowly moving or small stream systems. The transient storage model (TSM) has been widely used for modeling of hyporheic exchange. TSM calibration, for hyporheic exchange, is typically used to estimate four parameters, including the mass exchange rate coefficient, the dispersion coefficient, stream cross-sectional area, and hyporheic zone cross-sectional area. Prior studies have raised concerns regarding the non-uniqueness of the inverse problem for the TSM, that is, the occurrence of different parameter vectors resulting in TSM solution that reproduces the observed in-stream tracer break through curve (BTC) with the same error. This leads to practical non-identifiability in determining the unknown parameter vector values even when global-optimal values exist, and the parameter optimization becomes practically non-unique. To address this problem, we applied the simulated annealing method to calibrate the TSM to BTCs, because it is less susceptible to local minima-induced non-identifiability. A hypothetical (or synthetic) tracer test data set with known parameters was developed to demonstrate the capability of the simulated annealing method to find the global minimum parameter vector, and it identified the “hypothetically-true” global minimum parameter vector even with input data that were modified with up to 10% noise without increasing the number of iterations required for convergence. The simulated annealing TSM was then calibrated using two in-stream tracer tests conducted in East Fork Poplar Creek, Tennessee. In conclusion, simulated annealing was determined to be appropriate for quantifying the TSM parameter vector because of its search capability for the global minimum parameter vector.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Diel mercury concentration variations in a mercury-impacted stream

Here, filtered and particulate mercury (Hg) and methylmercury (MMHg), and associated water chemistry parameters, were evaluated bi-hourly for several 30 h periods during the summer and winter seasons at several distinct locations (downstream forested, midstream urban/suburban, upstream industrial) along a creek contaminated with high levels of inorganic Hg to determine if biogeochemical Hg and MMHg cycles respond to the daily photocycle. In summer particulate Hg and MMHg concentrations doubled overnight (excluding the upstream industrial site) concurrent with increases in turbidity and total suspended sediment; no such pattern was evident in winter. Seasonal and diel changes in the activity of macrobiota affecting the suspension of contaminated sediments are likely responsible for these patterns as other potential explanatory variables (e.g., instrument drift, pH, discharge) could not account for the range and timing of our observations. Diel patterns in filtered Hg (Hg D ) were significant only at locations and times of the year when channel shading was not present and daytime concentrations increased 22–89% above nighttime minima likely caused by direct and indirect photochemical reactions. Relationships between Hg D and dissolved organic carbon (DOC) concentration or character were inconsistent between sites. Unlike Hg D , there were significant diel patterns in filtered MMHg (MMHg D ) at all sites and times of year, with summer concentrations peaking in mid to late afternoon while the timing differed in winter, with concentrations peaking after sunset. Daily variability in MMHg D concentration ranged between 25 and 75%. The results imply key controls on net methylation occur within the stream or on the stream bed and include factors such as small-scale temperature changes in the water column and photosynthetic activity of stream biofilm. With respect to stream monitoring, results from this study indicate (1) consistent timing in stream Hg and MMHg sampling is required for accurate assessment of long-term trends, (2) in situ measurements of turbidity can be used to quantify diel dynamics of both particulate Hg and MMHg concentrations, and (3) in situ fluorescing dissolved organic matter (FDOM), a potential proxy for DOC, was not capable of resolving diel dynamics of filtered Hg or MMHg.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Joint estimation of biogeochemical model parameters from multiple experiments: A bayesian approach applied to mercury methylation

Here, to characterize complex biogeochemical systems, results from multiple experiments, where each targets a specific subprocess, are commonly combined. The resulting datasets are interpreted through the calibration of biogeochemical models for process inference and predictions. Commonly used calibration approaches of fitting datasets from individual experiments to subprocess models one at a time is prone to missing information shared between datasets and incomplete uncertainty propagation. We propose a Bayesian joint-fitting scheme addressing the above-mentioned concerns by jointly fitting all the available datasets, thus calibrating the entire biogeochemical model in one go using Markov Chain Monte Carlo (MCMC). The identification of null spaces in the parameter distributions from MCMC guided the simplification of certain subprocess models. For example, fast kinetic sorption was replaced by equilibrium sorption, and Monod demethylation was replaced by first-order demethylation. Joint fitting of datasets resulted in complete uncertainty propagation with parameter estimates informed by all available data.

54 ENVIRONMENTAL SCIENCES↗